( Reaffirmed 2003 ) Electroplating Chairman DR S. KRISHNAMURTHY Chemicals Sectional Committee, CDC 43 Zbpresenthg Indian Tel&one Industries Ltd, Bangalore Members Ministrj'oi D6fenc.e ( DGI ) SHRIJ. P. AOARWAL SWU MA~AWLAL ( Alternate ) Hindustan Copper Ltd. Calcutta DR S. I& BWWAS CHEMIST A N D METALLUROIST,Ministry of Railways INTEGRAL Coacn FACTORY, MADRAS CHEMIST &No METALLURGIfl II, RDSO, LUCKNOW ( Alternate ) Directorate General of Technical Development, SHRIR. D. KAWATRA New Delhi Phoenix Chen&al Works Pvt Ltd. Bombay SHRI M. A. KOTIBHASKAR SHRI M. A. CHUNEKAR ( Alternate ) Bharat Heavy Electricals Ltd, Bhopal DR V. S. MEHTA SHRIA. D. CHELVARAI ( Alternate ) T. I. Cycles of India, Madras SHRIS. PANCHAPAKE~AN SHRI R. VENKATARAMAN ( Alternate ) Hindustan Zinc Ltd, Udaipur DR B. R. L. Row SHRIG. L. JETWANI ( Alternate ) The Kesar Sugar Works Ltd, Bombay SHRI D. C. SHAH Ronuk Industries Ltd. Bombay SHRI R. A. SHAH KUMARIMRIDULAA. SHAH ( Alternate ) CentralElectro-Chemical ResearchInstitute (CSIR ., ). SHRI B. A. SHENOI Karaikudi DR N. V. PARTI-IASARDHY ( Alternate ) Golden Chemicals Pvt Ltd, Bombay SHRIL. H. THAKKAR SHRI Y. M. RAVAL ( Alternate ) SHRI M. V. MALLYA ( Alternate ) ( Continrrcd on page 2 ) Q INDIAN Copyright 1978 - STANDARDS INSTITUTION This publication is protected under the Zndiorr Copyright Act ( XIV of 1957 ) and reproduction in whole or in part by any means except with written permission of the publisher shall be deemed to be an inf&qomant of copyright under the said Act. 1 Members SHRI V. THIAOARAIAN DR G. AI. SAXENA, (Smah Scale Iadus- Director (Chem ) Secretary SHRI G. P. SARWWAT Deputy Director ( Chem ), ISI Precious Metal Salts Subcommittee, Convener SERI R. A. SfIAH CDC 43: 1 Ronuk Industries Ltd, Bombay Members Ministry of Defence ( DGI ) SHRIJ. P. A~ARWAL SHRI MADANLAL ( Alternate ) Arora-Matthey Ltd, Calcutta SARI B. P. ARORA SHRIS. P. ARORA ( Alternate ) Indian Telephone Industries Ltd, Bangalore DR S. KRE~-INAMURTHY ' Central Elcctro-Chemical Research Institute (CSIR), SHRIS. R. NATARMAN Karaikudi Hindustan Machine Tools ( Watch Division ), SHRIS. RAMACHANDRAN Bangalore Bharat Electronics Ltd, Bangalore SHRI M. K. SADAOOPAN Machsons Pvt Ltd, Bombay DR S. K. SONAWALA SHRI M~LCHANDMANILAL ( Alternate ) Indian Standard SPECXFICiTION FOR SILVER NITRATE, PURE AND ANALYTICAL REAGENT ( First Revision ) 0. FOREWORD ( First Revision ) was adopted by the Indian Standards Institution on 17 October 1977, after the draft finalized by the Ektroplating Chemicals Sectional Committee had been approved by the Chemical Division Council. 0;2 This standard was first published in 1962 -under the title `Specification for silver nitrate, technical and analytical reagent'. Later, with the publication of IS:2318-1974* and imposition of more stringent requirements by other user industries, the Sectional Committee decided to revise the standard and bring it in line with current staridards. 0.3 For the purpose of deciding whether a particular requirement of this standard is complied with, the final value, observed or calculated, expressing the result of a test or analysis, shall be rounded off in accordance with IS:2-1960t. The number of significant places retained in the rounded off value should be the same as that of the specified value in this standard. 1. SCOPE . 0.1This Indian Standard 1;lThis standard prescribes requirements and methods of sampling and test for silver nitrate suitable for use in electroplating and other chemical processes ( other than photofilms_production ) and as analytical reagent. 2. GRADES 2.1 There shall be two grades of the material as follows: a) Pure Grade - suitable for electroplating, silvering of mirrors and other processes, other than photofilms, and b) Analytical Reagent Grade - suitable for use in chemical analysis. *Specification for silver nitrate, photographic grade ( fiat rcrision). TRules for rounding off nynerical values ( revised ). 3 : 3, I&QUIBEMENTS 6 3.1 Description - The material shaP he in the fmm of colourless crystals material shall free from dirt, foreign matter and correspond in composition essentiail . 3.2 The material shall also comply with th+._mi@cments prescribed .in Table 1 when tested according to the m&hods .pt&&ed in Appendix A. Reference to the relevant clauses of Appendix A is given in co1 5 of the table. TABLE 1 REQUIREMENTS FOR PURE AND ANALYTICAL SILVER NITRATE, REAGENT : . ( Clauses 3.2 and B-5.1 ) CHARACTERISTIC REQUIREMENT L METHODOF TEST REP TO CL No. IN APPENDIXA Pure Grade Anaiyticai Reagent Grade (4) 99.9 0.003 0.05 0'001 0.0002 0~0003 O-0005 0.0025 (1) i) ii) iii) iv) v) vi) vii) (2) Silver nitrate ( as AgNO, ), percent by mass, Min Matter insoluble by mass, Max in water, percent (3) 998 0.001 0.02 L (5) A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 Alkalis and other metals ( as sulphates ), percent by mass, Max Bismuth and lead ( as Pb ), percent by mass, Max Co&r; ( as Cu ), percent by mass, Iron (as Fe), percent by mass, MUX Chloride MaX ( as Cl ), percent by mass, SO, ), percent .by Su~lpl&e&avas ix) Matter insoluble in alcohol To pass the test 4. PACKING AND MARKING 4.1 Packing - The material shall be packed in suitable dark coloured airtight containers as agreed to between the purchaser and the supplier. 4 The containers, and ais legibly and ind&b@ &th .w&vd potiible, a) Name, grade and net rnti of the titer&l; b) Name of the manufactizrer or his racogniaed trade-matk, if any; c) `Date of manufacture and'lot number t6 enable ihe material to be traced from records. 4.2.1 The material may also be marked with the ISI Certification Mark. Nom-The use of the IS1 Certification &lark is governed by the provisions of t,he Indian Standards Institution ( Certification Marks ) Act and the Rules and Regulations made thereunder. The IS1 Mark on products covered by an Indian Standard conveys the assurance that they have been produced to comply with the requirements of that standard under a well-defined system of inspection, testing and quality control which is deeed ati supervised by IS1 and operated by the producer. IS1 marked products are also continuously checked by IS1 for conformity to that standard aa a furtW -aafegaard. Details of conditions under which a licence for the use of the ISI Certitication Mark may be granted to' manufactyrers or processors, may be obtained from the Indian Standards Institution. 5. SAMPLING 5.1 The method of preparing representative samples of the material and criteria for its conformity with this specification shall be as prescribed in Appendix B. APPENDIX (Clause 3.2 ) A METHODS OF TEST FOR SILVER NITRATE, PURE AND ANALYTICAL REAGENT A-l. QUALITY OF REAGENTS A-l.1 Unless specified otherwise, pure chemicals and distilled water ( see IS: 1070-1977; ) shall be used in tests. NOTE- `Pure chemicals' shall mean chemicals that do not contain impurities which affect the results of analysis. A-2. DETERMINATION OF SILVER NITRATE A-2.1 Reagent A-2.1.1 Dilute Hydrochloric Acid - approximately 5 N. *Specification for water for general laboratoiy use ( secondrCvWm ). at 130f2"C to constant mass. 118*5xM, M 9 A-2.3 Calculation Silver nitrate ( as AgNO, ), percent by mass = where M, = mass in g of the precipitate, and Ma = mass in g of the material taken for the test. . A-3. DETERMINATION OF M&IT&R INSOLUBLE IN WATER A-3.1 Procedure - Weigh accurately 20 g of the material and dissolve in 100 ml of water. Filter the solution thrpugh a tared sintered glass crucible ( G No. 4 ) and wash the residue thoroughly with water. Dry the residue at 105-+2"C to constant mass and calculate percentage of residue by mass of the material taken for the test. NOTE- Dilute the filtrate and washingsto 200 ml in a volumetric flask and reserve it for further tests ( see A-4 ). A-4. DETERMINATION A-4.1 Reagents OF ALKALIS AND OTHER METALS approximately 5 N. A-4.1.1 Dilute Hydrochloric Acid - A-4.1.2 Concentrated Sulpkuric Acid - See IS : 266- 196 l*. A-4.2 Procedure - Dilute 100 ml of the solution ( see A-3.1, Note ) to 300 ml with water, heat to boiling and add sufficient dilute hydrochloric acid (about 12 ml ) to precipitate the silver completely. Set aside overnight, filter, evaporate the filtrate to dryness, moisten the residue with a few drops of dilute hydrqchloric acid, dilute with 10 ml of water, boil and filter. Add a few drops of concentrated sulphuric acid to the filtrate, evaporate to dryness, ignite gently and weigh. NOTE Reserve the residue for determination of copper ( A-6 ). A-4.2.1 The material shall be taken to have satisfied the requirement of the test if the mass of residue does not exceed 5 mg. *Specification for sulphuric acid ( rev&&). 6 ls : 2214 1979 A-5. lkli3SRbf~~TI0N A-5.1 BGIpats 0F BE .AWBL&UB A-5.1.1 Ammonium Citrate Solution - Dissolw 100 g of citric aoid in 250 ml of water and make alkaline with strong ammonia sobttiori using phenol red paper as indicator.' Fin&y dibte wit& water to p&u& 500 ml. A-5.1.2 Potassium Cyanide Solution - 10 percent ( m/v ). 1.25 percent ( m/v ). A-5.1.3 Sodium Metabisulphite Solution - A-5.1.4 Dithizone So!ution - 0902 percent ( m/v ) in chloroform. 1 N prepared by diluting A-5.1.5 Dilute Perchloric Acid -approximately 82 ml of perchloric acid ( r.d. 1.70 ) in 1000 ml with water. 6 N, prepared by A=&&& Dilute Ammonia Solution -approximately diluting. 280 ml of strong ammonia solution ( approximately 18 N ) to 1000 ml with water. A-5.1.7 Standard Lead Solution - Dissolve 160 g of 50 ml of concentrated nitric acid and dilute to 1000 ml volumetric flask. Further dilute 10 ml of this solution another volumetric flask just before use. One millilitre solution is equivalent to 0.01 mg of lead ( as Pb ). lead nitrate in with water in a to 1000 ml in of this diluted A-5.2 Procedure - Dissolve 5.0 g of the material in 30 ml of water in a separating funnel and add 4 ml of ammonium citrate solution, 10 ml of potassium cyanide solution and 5 drops of sodium metabisulphite solution. Extract with 3 successive 5 ml portions of dithizone solution. The final extract should be green; if it is not, continue extracting with 5 ml portions of dithizone solution until the last extract is green. Discard the aqueous solution. Combine the extracts in another separating funnel, add 10 ml of dilute perchloric acid, shake for 1 minute and discard the organic layer. To the aqueous extract add Q5 ml of ammonium citrate solution, 5 drops of sodium metabisulphite solution, 3 ml of dilute ammonia solution and 5 ml of potassium cyanide solution and adjust the solution pH between 9 and 10, if necessary by adding a few drops of dilute ammonia solution. Add dithizone solution in increments of 0'2 ml from a 10 ml micro-burette, shaking vigorously after each addition, until the organic phase is no longer red but has a mauve colour indicating the presence of a slight excess of dithizone. Prepare a blank following the above procedure, but omitting the sample and add to this, finally, the volume of dithizone solution as was added to produce the mixed colour in the test solution. Titrate the blank with standard lead solution, shaking vigorously between each addition of titrant, until the colour of the organic layer matches that of the organic layer of the test solution. A-5.2.1 The sample shall be taken as having satisfied the requirement of the test if not more than 5 ml of standard lead solution are required. 7 IS : 2214 - 1977 A-6. DETERMINATION A-6.1 Reagents A-6.1.1 Concentrated Hydrochloric Acid - approximately 11 N. OF COPPER A-6.1.2 Diethylammonium Diethyldithiocarbamate ( m/v ) in carbon tetrachloride. Solution - 0'1 percent A-6.1.3 Standard Copper Solution-Dissolve 3.93 g of cupric sulphate in 200 ml of water, add with stirring 50 ml of concentrated sulphuric acid, cool and dilute with water to 1000 ml. Further dilute 1 ml of this solution One millilitre of the diluted solution is equivalent to 100 ml with water. to 0.01 mg of copper ( as Cu ). A-6.2 Procedure-To the residue from the test for alkalis and other metals (see A-4.2, Note ), add 1 ml of concentrated hydrochloric acid and 1 ml of water, cover with a watch glass and digest on a steam bath for 20 minutes. Cool and dilute with water to 50 ml. Use the solution for test in A-6.2.1 and A-7.2. A-6.2.1 Transfer 25 ml of the above solution to a separating funnel with 5 ml of diethylammonium diethyldithiocarbamate solution. Carry out a control test by ~extracting similarly 25 ml of water, 1 ml of concentrated hydrochloric acid, 1 ml of standard copper solution and 5 ml of diethylammonium diethyldithiocarbamate solution. A-6.2.2 The material shall be taken as having met the requirement of the test if the colour produced in the test is not deeper than that in the control test. A-7. DETERMINATION A-7.1 Reagents A-7.1.1 Dilute Hydrochloric Acid -approximately A-7.1.2 A-7.1.3 A-7.1.4 5 N. 0.1 N. 7.5 M. in equal volumes. OF IRON - Potassium Permanganate Solution-approximately Ammonium Thiocyanate Solution -approximately Mixture of Amy1 Alcohol and Amy1 Acetate- A-7.1.5 Standard Iron Solution - Dissolve 0,702 g of ferrous ammonium sulphate [(NH,),SO,.FeS0,.6H,O] in water containing 10 ml of concentrated sulphuric acid and dilute with water to 1000 ml. Then dilute 10 ml of this solution to 1000 ml just before use (one millilitre of this diluted solution is equivalent to 0.001 mg of iron as Fe). A-7.2 Procedure -Transfer 15 ml of the solution prepared in A-6.2 to a 50 ml Nessler cylinder, add 2 ml of dilute hydrochloric acid, 1 drop of 8 potassium permanganate solutiou `.inriff. h&i. S ml of ammonium t&~~auate solution and 10 ml of the @xture of, amy1akohol and amyl a&t&e, shake vigorously and allow &a f&&s to seP&te: Carry out a mol test in another Ncssler cylinder~u&r&9'&8i of s&&i@ iron solution and 6 ml of water in place of the sample and proceed as above. A&7.2.1 The material shall be taken as having satisfied the requirement of the test if the red colour produced with the material is not deeper than that produced in the control test. A-8. DETERMINATION A-g.1 Reagents A4i.l.l Dilute Ammonia Solution -approximately 6 N. Prepare by diluting 280 ml of strong ammonia solution (approximate 18 N ) to 1000 ml with water. A4.1.2 Dilute Nitric Acid-approximately 5 N. Prepare 320 ml of concentrated nitric acid with water to 1000 ml. A-8.1.3 Silver Nitrate Solution - 0.2 `percent ( m/v ) . A-8.1.4 Standard Chloride Solution -Weigh ac&rately 0.165 0 g of sodium chloride, dissolve in water in a 1 000-m] volumetric flask and make up the volume. Further dilute 10 ml of this solution to 100 ml. One millilitre of this diluted solution is equivalent to 0'01 mg of chloride ( as Cl). 2 g of material of Analytical Reagent Grade A-8.2 Procedure -Dissolve or 1 g of pure grade material in 35 ml of water and add a measured volume of dilute ammonia solution until the precipitate just redissolves ( about 6 ml ): Electrolyze immediately with a starting current of 1A for one hour, protecting the solution from contamination from the atmosphere. Make the solution slightly acid with dilute nitric acid, add 1 ml of acid in excess and transfer to a 50-ml Nessler cylinder. Rinse the beaker and finally dilute the contents in the Nessler cylinder to 50 ml mark. In another 50-ml Nessler cylinder mix 1 ml of standard chloride solution with the same volume of dilute ammonia solution as used above, neutralize with dilute nitric acid, add 1 ml in excess and dilute to 50-ml mark with water. Finally add 1 ml of silver nitrate solution to each of the two Nessler cylinders. CAUTION - The ammoniacal solution of silver should be electrolyzed immediately to avoid the formation of dangerously explosive compounds of silver with nitrogen. A-8.2.1 The material shall be taken to have satisfied the requirement of the test if the opalescence produced with the material is not greater than that produced with standard chloride solution. 9 by diluting OF CHLORIDE , carrying out this 8&et a p&u$uuy A-R0 Geueral -In sulphate is corisidered necessary and. hence chruzpit~ been prescribed. aqaration of procedure bag A-9.1 Apparatus -The apparatus consists of a glass tube approximately 15 cm long and 1.5 cm in diameter, joined to an outlet approximately 10 cm long and 0.5 cm in diameter through a stop-cock. The outlet enters a The flask is connected to .a filter flask through a bored rubber stopper. filter pump. A-9.2 Reagents . 1 N ( see A-5.1.5 ). 1 N and 5 N. 1 N and 0.1 N. A-9.2.1 Dilute i"erchloric Acid - approximately A-9.2.2 Chromatographic Grade Alumina A-9.2.3 Dilute Hydrochloric Acid - approximately A-9.2.4 Dilute Ammonia Solution -approximately A-9.2.5 Denatured Spirit - See IS : 324-1959*. A-9.2.6 Barium Chloride Solution 12 percent ( m/v ). A-9.2.7 Standard Sulphate Solution -prepared by diluting 20.8 ml of 0.1 N sulphuric acid with water 1000 ml. One millilitre of this solution is equivalent to O-1 mg of sulphate ( as SO, ). A-9.3 Preparation of Clwomatograptdc Cohmm -Mix 250 g of chromatographic grade alumina with 500 ml of dilute hydrochloric acid and allow to stand for 1 hour with occasional stirring. Wash free from fines by repeated decantation with water until supernatant liquid is almost clear after standing for 1 minute. Filter with suction to remove excess water and dry it in an oven at 110°C. Sift the dried material and reject the portion that passes 75-micron IS Sieve. A-9.3.1 Plug the column above the tap with glass wool and fill it to a height of 10 cm with a slurry of the prepared alumina. Then wash successively with 50 ml of 1 N dilute ammonia solution and,twice with 25 ml of 0.1 N dilute ammonia solution and flnafly with 50 ml of water. A-9.4. Procedure -Dissolve 2 g of material of Analytical Reagent Grade and 05 g of Pure Grade in 50 ml of dilute perchloric acid. Regenerate the column ( see A-9.3.1 ) by passing through it 50 ml of dilute perchloric acid and pass the prepared solution of the material through the column at 8 rate of 10 to 15 ml per minute. Elute `with 50 ml of dilute perchloric acid, wash with 30 ml of water. 1Wash out the receiver, rejecting the contents, and place in it 2.5 ml of 5 N dilute hydrochloric acid. Pass through the *Specification for denatured spirit ( m&d). column 10 ml of 1 N dilute ammonia solutfan rrrr9$.&en 26 ml of 0.1 N dilute ammonia solution, collecting the eluate, .To the receiver add 10 ml of denatured spirit, mix, add 1 ml of bar&& &lo&e `ablution, mix immediately- and allow to stand for 1 hour. Carry out a con&W test -using 05 ml of standard sulphate solution for Analytical Reagent Grade and 1 ml for Pure Grade, with 37 ml of water, 10 ml of denatured spirit, and 1 ml of dilute hydrochloric acid, mixing together, followed by 1 ml of barium chloride solution, mixing and allowing to stand for 1 hour. A-9.4.1 The material shall be taken as having satisfied the requirement of the test if the turbidity produced with the material is not greater than that produced in the control test. ' A-10. TEST FOR MATTER `A-10.1 Reagent A-10.1.1 Penatured Spirit INSOLUBLE IN ALCOHOL See IS: 3241959*. A-10.2 Procedure - Dissolve 0.5 g of the material in O-5 ml of water and add 20 ml of denatured spirit. A-10.2.1 The material shall be taken as having satisfied the requirement of the test if the solution obtained is clear and colourless. APPENriIX ( Clause 5.1 ) SAMPLING B OF SILVER NITRATE, PURE AND ANALYTICAL REAGENT B-l. GENERAL REQUIREMENTS B-1.0 In drawing, preparing, storing and . follotiing precautions shall be observed. handling test samples, the B-l.1 The sampling instrument and the containers for samples shall be such that the material has no action on them. They shall be clean and dry. B-l.2 Samples shall be stored in such a manner that the temperature of the material does not vary unduly from the normal temperature. As far as possible, the material shall also be protected from light. *Specification for denatured spirit ( revised ). s2, `SCALE OF SAMPLING B-2.1 Lot - All the containers in a single cort@gnment of the same grade of material drawn from the same batch of mam&&re shall constitute a lot. B-2.2 For ascertaining the conformity of the material in any lot to the requirements of this specification, samples shall be tested for each lot The number of containers to be selected at random from lots separately. of different sizes shall be in accordance with Table 2. TABLE NUI~BEROF CONTAINERS IN THE LOT up to 25 26 51 151' ,, ,, 50 150 300 3 4 5 6 8 2 SCALE OF SAMPLING . SAMPLE SIZE ,, 301 and above B-2.3 The containers shall be selected at random. In order to ensure randomness of selection, a random number table shall be used. For guidance and use of random number table, IS : 49051968* may be referred. fe ;i&dabsence of a random number table, the following procedure may from any container in the lot, count them as 1, 2, etc, up to r and so on, where r is the integral part of N/n $`?be%~ the number of containers in the lot and n the sample size) Every rth container thus counted shall be withdrawn so as to cons: titute the required sample size.' B-3. INDIVIDUAL AND COMPOSITE SAMPLES `Starting B-3.1 From each of the containers selected according to B-2.2 and B-2.3 a representative portion of the material sufficient for the tests shall be withdrawn. These samples, representing each of the selected containers, are termed as individual samples. B-3.2 From each of the ,individual samples, a small but equal quantity of the material shall be taken. Such portions shall be thoroughly mixed to give a composite sample. *Methods for random sampling, B-3.3 The material constituting each of the the composite sample shall be stored sepa partklzlars. B4. NUMBER OF TESTS B-4.1 Test for silver nitrate samples. content shall be `conducted s ,well as &cation on individual B-4.2 Tests for the remaining characteristics sample. . B-5. CRITERIA FOR CONFORMITY shah be done on composite B4.1 For Individ~ Samples -_ For silver nitrate content, the test results shall be noted and their mean (X) and the range ( R),being the difference bQhvem the maximum and mini.tium of test rust&s, shall be computed. For declaring the conformity of the lot in respect of silver nitrate content, ( g--O.6 R ) shall be greater than or equal. to the minimum specified in Tabk 1. B-S.2 For Composite Sample - For declaring the conformity of the lot to the requirements of all other characteristics, the test results of the composite sample shall satisfy the relevant requirements specified in Table 1. INDIAN ON STANDARDS ELECTROPLATING CHEMICALS IS : Chromium trioxide ( firsf revision ) 330-1968 1809-1968 Nickel salts for electroplating ( first revision ) 1880-1977 Zinc oxide and zinc salts for electroplating ( firsi revision ) 2214-1977 Silver nitrate, technical and analytical reagent ( first revision ) 3026-1968 Tin salts for electroplating ( jirsr revision ) 4846-1968 Sodium potassium tartrate ( Rochelle salt ) 4847-1968 Copper cyanide for electroplating 5003-3968 Cadmium oxide for electroplating 5761-1970 Gold cyanide and gold potassium cyanide for electroplating 6267-1971 Silver cyanide and silver potassium cyanide for electroplating 6358-1971 Potassium and sodium cyanides for electroplating 6588-1972 Gold chloride ( chlorauric acid ) 7038-1973 Chloroplatinic acid ( platinic chloride ) 7067-1973 Fluoboric acid and metal fluoborates for electroplating 8590-1977 Indium sulphate for electroplating